Sulfobenzamides



2,694,718 Patented Nov. 16, 1954 SULFOBENZAMIDES Ilmari Salminen and Arnold Weissberger, Rochester,

N. Y.,"assignors to Eastman Kodak Company, Roch ester, N. Y., a corporation of New Jersey No Drawing. Application December 5, 1951,

. Serial No. 260,099

2 Claims. (Cl. 260-310) This invention relates to the preparation of sulfobenzamides and sulfopropionamides and particularly to thegreparation of o-sulfobenzamides and fl-sulfopropionami es.

Anhydrides such as o-sulfobenzoic anhydride have been described in the literature. However, little is known of the reactions of the anhydride with primary aromatic amines. Am. Chem. J. 17, 317, 339, 347; 18, 804, indicate that aniline reacts to form asym. or sym. compounds neither of which contain free sulfonic acid groups. Am. Chem. J. 20, 127, shows that sulfonphthaleins are obtamed with dimethyl or diethylanilines. Other references disclose that aniline and toluidine give the corresponding ammonium salts of the sulfoamides. Nowhere is there any indication that it would be possible to react the anhydride with aromatic amines to directly obtain a benzamide containing a free sulfo group. The teachings are that a sulfonic acid salt would be obtained which would have to be neutralized to liberate the free acid.

Similarly, little is known of the reactions of the corresponding aliphatic anhydrides e. g. fi-sulfopropionic anhydride. As above, the indications from the prior art are that when the anhydride is reacted with aromatic amines, sulfonic acid salts would be obtained.

We have discovered that the mentioned anhydrides are particularly eflicacious for use in the preparation of coupler compounds of especial value in color photography. In certain cases in processes and products for color photography it is desirable that the coupler compounds contain in their molecule SO H groups which increase the solubility of the compounds and in other cases such as in emulsion layers actually tend to prevent diffusion of the coupler compound in the emulsion possibly by virtue of the SO H group attaching itself to basic groups in the colloid vehicle of the emulsion.

During the preparation of the couplers by reacting the anhydrides with coupler compounds containing amino groups, it became apparent that a particularly advantageous process was under consideration. That is, it had been supposed that in a typical reaction between o-sulfobenzoic anhydride and a coupler i O HaN- coupler two molecules of the latter compound would be required to provide for formation of the amide group and the salt of the sulfonic acid group. However, it was found that regardless of the quantity of amino coupler used no coupler amine salt was obtained. Accordingly, to obtain the free acid form of the coupler equimolecular parts of the reactants could be used. and it was not necessary to use a neutralizing step to free the sulfonic acid group in the coupler as had been expected.

The compounds of our invention have the general formula in which R is either a mononuclear 2-sulfo-1-arvl group of the benzene series or a p-sulfoethyl group, and Y represents a group of atoms containing a group reactive with the oxidation products of a primary aromatic amino silver halide developing agent c. g. a S-pyrazolone group having a methylene group in the 4-position which will couple in the presence of exposed silver halide with the oxidized form of the developing agent which results from reduction of the silver halide, to form a dye in situ.

For illustration, the least complex compounds of our invention can be made by reacting the o-sulfobenzoic anhydrides or fl-sulfoalkyl anhydrides with simple coupler compounds such as o-aminophenols, 3-amino-S-pyrazo-. lones or couplers containing the group -CO-CH2CO-- and a terminal NH2 group. Thus o-sulfobenzoic anhydride yields the following compounds when reacted with o-aminophenol, 3-amino-5-pyrazolone and a-benzoyl-pamino-acetanilide, respectively SOaH Accordingly, compounds of this type having the o-sulfo aryl group are prepared by our process whereas other methods such as sulfonation cannot be used particularly since sulfonation does not introduce the sulfo group into the right position or has undesired effects upon the coupler compound. It might be thought that o-sulfobenzoyl dichloride would yield amides comparable to those of the invention when reacted with a coupler containing an amino group. However, the literature Ber. 31, 1648 (1898) indicates that this diacid chloride does not form o-sulfobenzoic acid amides.

Similar compounds are obtained when the corresponding aliphatic anhydrides such as [i-sulfopropionic anhydride is used for reaction with the coupler compound containing an amino group.

A preferred group of compounds have the general structure in which R represents a mononuclear aryl group of the benzene series, D represents a mononuclear 2-sulfo-1- aryl group of the benzene series and Y is as above a group of atoms containing a reactive phenolic hydroxyl or methylene group, is obtained by reacting an ortho-sulfobenzoic acid anhydride with a coupler amine having the formula form a sulfonic acid salt the free acid form of the coupler can be obtained by neutralization.

The compounds of the invention may be further classified as having the general formula in which R, R R and R each represent hydrogen, alkvl or arvl groups of the benzene series and R, R R and R The aromatic anhydride'sused have the preferred general- -formula sor Thepreferred aliphaticsanhydride's:used in-our ln-:.

vention have the general formula in which R, R1 and 'Rzare either hydrogen or alkyl groups such as fi-sulfopropionic and fl-sulfo'isobutyric anhydride. These anhydrides can be obtained by reaction of aliphatic acids such as propionic valeric, capric, caprylic, caproic, isobutyric; etc-..acids--.with.sulfuryl chloride.

The following examples illustrate our invention.

Example I 1-.phenyl-3-amino-5-pyrazoloneis reacted withmnitro-benzoyl. chloride,- the :resultant amide :redticed with hydrogen and the resulting amino group reacted witlL 2.-(2,4'-diamylphenoxy)-5mitrobenzoyl chloride The nitro group of the resultant product ;is'-then reduced-"to. obtain 1-phenyl-3-{3' [!-amino-2f'-(2,4-di-tert. amylv phenoxy)-benzamido]-benzamido} 5-pyrazolone.

In a flask is placed 300 volumes of dry toluene. This is heated to boiling and initis dissolved 3.5 parts of "lphenyl-3{3'-[5"-amino-2-(2,4-di-tert. amylphenoXy)- benzamido]-benzamido}-5-pyrazolone. In a flask is dissolved 1 part of o-sulfobenzoic anhydride in 7.parts. of hot dry toluene. This solution is added rapidly with. stirring to the boiling solution of the amine; The mix ture becomes cloudy andthe stickyproddct. is deposited on the;walls of the flask? The.reaction'is"assisted"by1 heating-Qua steam bath with stirring fo'r oneqhour."v It' is then cooledto room temperature undercoldrunning water and the solidified productfis broken up with a stirring rod. It is separated by filtration and washed. with petroleum ether and dried; Thessolidis crushed in a mortar to a'fine powder," suspended iin' petroleumetheraand filtered and dried." The productxis'robtained. as a tan powder.

Example: :2.-

Nnco-i3- QOOCHZCONHQNHCDQK 61H;

on. auto.

CIHu

e-2-methoxybenzoyl=4-amino zanethoxyacetanilide-iszee acted with 2-(2:,'4'-di-tert: iarnyl phenoxy )--:5-11itro benzoyl? ChlOTldQ; the mtro groupiof the iamidezproduct isfthen: reduced "and rthe resultant coupler amine r1'63CtCd1WiihI 0- sulfobenzoic anhydride as follows:

To a warm (50) solution o=:.1'.:part:of. amirieainrll)? 4:. volumes of benzene is added a solution of 1 part of o-sulfobenzoieanhydridein- 20-volumes of warmbenzene. The pale yellow solution is heated for 20 minutes at the boiling point and then allowed to stand for 24 hours at room temperature. The light yellow product which separates .is filtered and washed on the funnel with 10 volumes'of beuzeue; M. P. l35-145. S Agalysis.---Calcd-.v for CnHarNsOroS: S, 3.8. Found:

Example. 3

CONHOHaCHz-QNH o o 12- hydroxyw- N (4"'- amidophenethyl)? 4-- chloro- 2-Tnaphthamide. is* reacted 3 withv 2-(2,4--di1 tert. .arnyl-' phenoxy) r5-"nit'r'obenzoyl chloride. in.. the. presence. of acetic acidandfisodiumacetate; The .nitrow group .of the resultantamide-is' reduced .and .the amino group. of the .resultant .coupler ..amine.reacted 'withLo-sulfob'enzoic anhydr'ide' .as .follows a.

To a .warm jsolutionnof 1.4 partsof thecoupler amide .in5 0 fivolumesof benzene is. added a. warm (50 solutionof .11.. part o-sulfobenzoic .anhydride .in- 40 lvolumes .oiibenzene... The reaction mixture is. heated 20 minutes on ,the steam-bath and. then. allowed .to standu48 hours at room temperature; The solution is concentrated at.reduced pressure.to a powderwhich' is trituratedwith three. 10;volume:portions of -etherfollowed by 10 volumes.o.petroleum..ether.. Akfleshacolored solid is obtained; Calcil for.:C4'9HsoClN3Oa'S: S,. 3.7. Found: S, 3.9;" While this coupler. .and .other COUPIEI'SzOf the invention-econtaint a. chldri.ne .atom. parato the hydroxyl group of..the.naphtl1o1-nucleus,.this. position. is. still. reactive..w1th;.the. color.developer.

To a hot solution of 4parts of the coupler'amine which was used in Example 2 for reaction with o-sulfobenzoic anhydride, in 200 volumes of benzene is added a solution of one part of the B-sulfopropionic' anhydride in 200 volumes of benzene. After standing overnight, the clear yellow solution 'is;dil11ted witht400 volumes of petroleum ether, after which the product separates as an oily solid.

Example 5 (lhHn To a hot suspensionof-4 parts of the pyrazolone used inyExample f1 formeaction with. o-sulfobenzoic ranhydride in 1200 "volumeswofn'benzene TSxBddCdzOIlGnPB-l't of. the p. sulfopropionic anhydrirle: :dissolved in. volumes .of. hot'benzene. The *l'HlXflll'fiClfifll'S .and-a-white' solid be ginsio separate. Themhrture is left overnight-and the produet;asolated-abwfiltratmna and dried.

ifitillisi i Example 6 "OH nacaemea so n 9 I v OONHCHQHrONHGQQ To a hot solution of 4.5 parts of e naPhtharhideused in Example 3 for reaction with o-s ulfobenzoic anhydride in 60 volumes of benzene is added a-solution of one part of fl-sulfopropionicanhydridein .60 volumes of benzene. The mixture forms a clear amber solution which is allowed to stand overnight. The product is precipitated by the addition of 1180'Jv'olumes of petroleum ether, filtered Example I counomcmmrooO In a round-bottom flask was placed 2.6 parts of 1- hydroxy-N-(fi arnino)ethyl-4-chloro-2-naphthamide compound in 220 volumes of chlorobenzene. Solution was effected by heating and to it was added a Warrnsolution of 2.0 parts of o-sulfobenzoic anhydride in volumes of chlorobenzene. The clear reaction solution was swirled thoroughly, stoppered and left standing overnight. A gummy solid which separated was filtered andj dried, 3.7 parts being obtained.

ANALYSIS Calculated tor omnnolNims mm This coupler gives a cyan dye when used in a developer containing a primary aromatic amino developing agent .fo an ex ose :s ve ha id .em lsi n-.-.-laxe .o whe 0 $0 11 In a .round bottom..flask under aanrefiux condensenovas 1 6 colored image resultsavhengthepoupler is used in an emulsion layer developed witha color developer.

'x mma e In a round-bottom flask under a reflux condenser was placed 2.5 parts of the amintg'eompoundaandlOO volumes of dloxane (No. 2144, storedaover sodium). Jo this solution was added with swirling 2.0 partsvof o-sulfobenzoic anhydride ,gli ss,olved in 10 volpmes of dioxane, a solid separating. The. mixt,ure;ygas heated ugder the reflux conilo placed a hot solution of 2.9 parts of the 1-phenyl-3-(3'- 1 aminobenzamido-j 5 pyrazolone and '50 volumes of dioxane. To it was added with swirling 1.8 parts of,o;sulo- .;b e nzoic anhydride dissolved'in 25fy olumes of dioxane.

The reaction mixture was heated under the reflux condenser for 10 minutes and allowed-1o cool. The product was.filtered,-.5.2 parts being obtained.

ANALYSIS Calc. for CuHiaN40aS Found This coupler used in a developer (for an exposed silver halide emulsion layer) containing a color developing agent, yields a magenta dye image having maximum light absorption at 520 m which showed very little fading when exposed to ultraviolet light and heat. A similar denser 'fQr algout l0 minute s and the clear supernatant port on removed by decanta tion from an oily residue. On cooling a solid, which-crystallized was filtered, two parts being obtained.

ANAIiYSIS I Calc. for qaHnNOS Found This coupler when usedin a'developer*ffor' an exposed silver halide emulsion layer) containing a color developmg agent, yields a yellow dyedmage having maximum light absorption at 448 mpwhich showed slightfading when exposed. to ultraviolet light and heat. ,Ayellow dye -3image also results awhen the 'goupler isin an {errlulsion -WhiCihjEi colordeveloped. r

' Example '10 The pyrazolone couplers Nos. 11, 12, 13 and 14 of the Graham U. S. patent application Serial No. 260,097 filed concurrently herewith and prepared as described in Ex- ;ample 6 thereof, are given as further examples of couplers conta ning anp-su lfophenylgroup. These couplers have the formulas N=C-NHCO (GHI)tO I C an l C r 0H, CIHH ll soil! 1 Example 11 The pyrazolone couplers Nos. 4 and 7 of the Salminen et a1. U. S. patent application Serial No. 260,100 filed concurrently herewith further exemplify the couplers of the invention containing o-sulfophenyl groups. These couplers have the formulas .L 8 What we claim is: 1. The method for preparing a compound having the general formula 5 omit-t. O NHCO-: coma-R om Q C v v '10 NH which comprises heating 2-sulfobenzo1c anhydride under Q= N SO H anhydrous conditions in an inert organic solvent for the Z-sulfobenzoic anhydride, with an amine having the gen- 6 eral formula a {H NHCO I $5Hu-t (iQrzHts V 0 NH, H1CCNHGO O= ILIT i i sHn-t. CONE-R A v 1 80m wherein R represents a monocyclic aryl group 'of the N I 1 benzene series containing a carbonamido group.

' -O 2. The method for preparing a compound having the I formula V OCmHn H:?-(fi-NHOO NHCO-- 1 phenyl 3 {[3 (2" sulfobenzamido) 4' octadec- 0:0 yloxy] benzamido} 5 pyrazolone. NHCO a0 Example 12 I f i 4 i a n .Coupler No. 4 of the Graham et al. U. S. patentapplication Serial No. 260,097 filed concurrently herewith further illustrates the couplers of this invention. This coupler has the structure 05H sotn NBC 0- N=oNHoo-- Nnoo- Ga t CO-CHN=N 1120000 COOCH:

51311) 7 Y .7 Other coupler molecules containing free amino groups which comprises heating 2-sulfobenzoic anhydride under which can be reacted with the anhydrides will occur to anhydrous conditions in toluene, with 1 phenyl 3 those skilled in the art, e. g. those disclosed in French {3'[5 amino 2" (2,4 di tert.amylphenoxy) Patent 836,144 or U. S. Patent 2,376,380. benzamido] benzamido} 5 pyrazolone.

As will be appali ent from the above exfilmpleshall 1of the compounds of t e invention contain eit er a p eno ic hydroxyl group (a phenol or nalphthol group substituted References Clted m the file of thls patent or not), or a -CHzgroup suc as present in a S-pyraza clone nucleus or in a COCH2--CO group of UNITED STATES PATENTS benzoylaceto or acetoaceto groups. In the formula Number Name Date RCONHY these groups are attached directly or in- 6,8 9 WllmanHS 1940 directly to the nitrogen atom. 4 Y

Thehcouplers of the inventirfm arelpartilcularly ulseful in FOREIGN PATENTS silver alide emulsion ayers or co or p otograp y. By virtue of the presence of the sulfo group, dispersion of the ggg Au gg I g, couplers 1n the aqueous emulsions 1s facllitated.

Thedcouplers areladvantafgeogsly[employed in glkaline 7 THER REFERENCES color eveloping so utions or eve oping expose multiv layer color films which may or may not contain other g fg g fi fi g i 28;;118569 clung Taverna coupler compounds in the emulsion layers. The color films with which the compounds are employed contain one or more emulsion layers sensitized to record the red,

green and blue light regions of the spectrum. 

1. THE METHOD FOR PREPARING A COMPOUND HAVING THE GENERAL FORMULA 